Prof Laura Herz FRS

Abstract:

The generation and control of terahertz pulses is vital for realizing the potential of terahertz radiation in several sectors, including 6G communication, security and imaging. In this work, we present the topological Dirac semimetal cadmium arsenide as a novel helicity-dependent terahertz source. We show both broadband (single-cycle) and narrowband (multi-cycle) terahertz pulses upon near-infrared photoexcitation at oblique incidence. By varying the incident angle of the photoexcitation pulse, control of the emission frequency can also be achieved, providing a candidate for a tuneable narrowband terahertz source.

Abstract:

The emergence of perovskite photovoltaic technology is transforming the landscape of solar energy. Its rapid development has been driven by the advances in our understanding of the thin-film microstructures of metal halide perovskites and their intriguing correlations with optoelectronic properties, device efficiency and long-term stability. Here we discuss the morphological characteristics of three key microstructure types encountered in perovskites, which include grain boundaries, intragrain defects and surfaces. To reveal detailed structural information of these microstructure types via tailored characterizations is crucial to probe their detrimental, neutral or beneficial effects on optoelectronic properties. We further elaborate the impacts of these microstructures on the degradation modes of perovskites. Representative examples are also presented, which have translated fundamental understandings to achieve state-of-the-art perovskite solar cells. Finally, we call for more attention in probing hidden microstructures and developing high-spatiotemporal-resolution characterizations, as well as harnessing the potential merits of microstructural imperfections, towards an elevated understanding of microstructure–property–performance relationships for the next solar cell advances.

Abstract:

I-V-VI₂ ternary chalcogenides are gaining attention as earth-abundant, nontoxic, and air-stable absorbers for photovoltaic applications. However, the semiconductors explored thus far have slowly-rising absorption onsets, and their charge-carrier transport is not well understood yet. Herein, we investigate cation-disordered NaBiS₂ nanocrystals, which have a steep absorption onset, with absorption coefficients reaching >10⁵ cm⁻¹ just above its pseudo-direct bandgap of 1.4 eV. Surprisingly, we also observe an ultrafast (picosecond-time scale) photoconductivity decay and long-lived charge-carrier population persisting for over one microsecond in NaBiS₂ nanocrystals. These unusual features arise because of the localised, non-bonding S p character of the upper valence band, which leads to a high density of electronic states at the band edges, ultrafast localisation of spatially-separated electrons and holes, as well as the slow decay of trapped holes. This work reveals the critical role of cation disorder in these systems on both absorption characteristics and charge-carrier kinetics.

Abstract:

Mixed-halide perovskites offer ideal bandgaps for tandem solar cells, but photoinduced halide segregation compromises photovoltaic device performance. This study explores the influence of a hole-transport layer, necessary for a full device, by monitoring halide segregation through in situ, concurrent X-ray diffraction and photoluminescence measurements to disentangle compositional and optoelectronic changes. This work demonstrates that top coating FA0.83Cs0.17Pb(Br0.4I0.6)3 perovskite films with a poly(triaryl)amine (PTAA) hole-extraction layer surprisingly leads to suppression of halide segregation because photogenerated charge carriers are rapidly trapped at interfacial defects that do not drive halide segregation. However, the generation of iodide-enriched regions near the perovskite/PTAA interface enhances hole back-transfer from the PTAA layer through improved energy level offsets, increasing radiative recombination losses. It is further found that while passivation with a piperidinium salt slows halide segregation in perovskite films, the addition of a PTAA top-coating accelerates such effects, elucidating the specific nature of trap types that are able to drive the halide segregation process. This work highlights the importance of selective passivation techniques for achieving efficient and stable wide-bandgap perovskite photovoltaic devices.